((5S,6R)-5,6-dihydroxycyclohexa-1,3-dien-1-yl)methyl acetate | 131043-51-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ((5S,6R)-5,6-dihydroxycyclohexa-1,3-dien-1-yl)methyl acetate
• 英文别名: cis-(1S,2R)-3-(Acetoxymethyl)cyclohexa-3,5-diene-1,2-diol；[(5S,6R)-5,6-dihydroxycyclohexa-1,3-dien-1-yl]methyl acetate
• CAS: 131043-51-1
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: VIFGTBOCRRBWFL-DTWKUNHWSA-N

物化性质

• 沸点：
  315.7±42.0 °C(Predicted)
• 密度：
  1.291±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ((5S,6R)-5,6-dihydroxycyclohexa-1,3-dien-1-yl)methyl acetate 在 对甲苯磺酸 作用下， 以 丙酮 、 甲苯 为溶剂， 生成 (1R,3S,4R,7S,8S)-ethyl 7,8-isopropylidenedioxy-1-(acetoxymethyl)-2-oxabicyclo[2.2.2]-5-octen-3-carboxylate
  参考文献：
  名称：

  Aza and oxo Diels–Alder reactions using cis-cyclohexadienediols of microbial origin: chemoenzymatic preparation of synthetically valuable heterocyclic scaffolds

  摘要：

  Aza and oxo Diels-Alder reactions using enantiopure cis-cyclohexadienediols were studied. These dienediols were obtained from the biotransformation of monosubstituted arenes using bacterial dioxygenases (toluene and benzoate dioxygenases). Ethyl glyoxylate and its N-tosyl imine were used as dienophiles to afford the corresponding hetero Diels-Alder bicyclic adducts with excellent regio- and stereoselectivities. Quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed to rationalize the observed selectivities especially the stereochemical aspects of the cycloadditions. The synthetic importance of these adducts is highlighted for the preparation of enantiopure 2,2,3,4,5,6-hexasubstituted piperidine and tetrahydropyran from toluene. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.10.015
• 作为产物：
  描述：

  乙酸苄酯 在 Pseudomonas putida UV₄ 、 氧气 作用下， 生成 ((5S,6R)-5,6-dihydroxycyclohexa-1,3-dien-1-yl)methyl acetate
  参考文献：
  名称：

  对映选择性甲苯双加氧酶催化单取代苯的二羟基和三羟基化

  摘要：

  使用甲苯二加氧酶（假单胞菌中存在的生物催化剂）对一系列单取代的烷基苯底物1A-1G进行生物转化期间，发生不对称的顺式-二羟基化反应生成二醇2A-2G和顺序的苄基单羟基化-顺式二羟基化反应生成三醇4A-4G（三羟基化反应）。putida UV4。R和S苄醇对映异构体3B-3D，3B'-3D'的双加氧酶催化的顺二羟基化反应得到相应的对映纯三醇4B-4D，4B'-4D'。底物1J–1L的生物转化产生顺式二醇2J–2L和次要的三醇代谢物4A。假定苯甲醇3J-3L为不稳定的中间体，通过苯甲醛5和苯甲醇3A中间体产生三醇4A。顺含有大体积基团（单取代的苄基片二羟基化1H，1I）或1,4-二烷基-取代的苯底物（图10A-10C），获得相应的顺式-dihydrodiol代谢物（2H，2I，11A-11C））。根据NMR和CD光谱，将顺式二醇2A-2L，11A-11C和三醇4A-4F，4B'-4D'立体化学分配为1

  DOI：

  10.1039/b000753f

文献信息

• Chemoenzymatic Synthesis of Advanced Intermediates for Formal Total Syntheses of Tetrodotoxin
  作者：Daler Baidilov、Lukas Rycek、John F. Trant、Jordan Froese、Brennan Murphy、Tomas Hudlicky

  DOI：10.1002/anie.201804602

  日期：2018.8.20

  Advanced intermediates for the syntheses of tetrodotoxin reported by the groups of Fukuyama, Alonso, and Sato were prepared. Key steps include the toluene dioxygenase mediated dihydroxylation of either iodobenzene or benzyl acetate. The resulting diene diols were transformed into Fukuyama's intermediate in six steps, into Alonso's intermediate in nine steps, and into Sato's intermediate in ten steps

  制备了由福山，阿隆索和佐藤小组报告的河豚毒素合成的高级中间体。关键步骤包括碘代苯或乙酸苄酯的甲苯双加氧酶介导的二羟基化。所得的二烯二醇经六步转化为福山中间体，经九步转化为阿隆索的中间体，并经十步转化为佐藤的中间体。
• Boyd, Derek R.; Sharma, Narain D.; Byrne, Breige, Journal of the Chemical Society. Perkin transactions I, 1998, # 12, p. 1935 - 1943
  作者：Boyd, Derek R.、Sharma, Narain D.、Byrne, Breige、Hand, Mark V.、Malone, John F.、Sheldrake, Gary N.、Blacker, John、Dalton, Howard

  DOI：——

  日期：——
• Enantiomeric excess and absolute configuration determination of cis-dihydrodiols from bacterial metabolism of monocyclic arenes
  作者：Derek R. Boyd、M. R. J. Dorrity、M. V. Hand、J. F. Malone、N. D. Sharma、H. Dalton、D. J. Gray、G. N. Sheldrake

  DOI：10.1021/ja00002a040

  日期：1991.1
• BOYD, D. R.;DORRITY, M. R. J.;HAND, M. V.;MALONE, J. F.;SHARMA, N. D.;DAL+, J. AMER. CHEM. SOC., 113,(1991) N, C. 666-667
  作者：BOYD, D. R.、DORRITY, M. R. J.、HAND, M. V.、MALONE, J. F.、SHARMA, N. D.、DAL+

  DOI：——

  日期：——
• Aza and oxo Diels–Alder reactions using cis-cyclohexadienediols of microbial origin: chemoenzymatic preparation of synthetically valuable heterocyclic scaffolds
  作者：Mariana Pazos、Sebastián Martínez、María Agustina Vila、Paola Rodríguez、Nicolás Veiga、Gustavo Seoane、Ignacio Carrera

  DOI：10.1016/j.tetasy.2015.10.015

  日期：2015.12

  Aza and oxo Diels-Alder reactions using enantiopure cis-cyclohexadienediols were studied. These dienediols were obtained from the biotransformation of monosubstituted arenes using bacterial dioxygenases (toluene and benzoate dioxygenases). Ethyl glyoxylate and its N-tosyl imine were used as dienophiles to afford the corresponding hetero Diels-Alder bicyclic adducts with excellent regio- and stereoselectivities. Quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed to rationalize the observed selectivities especially the stereochemical aspects of the cycloadditions. The synthetic importance of these adducts is highlighted for the preparation of enantiopure 2,2,3,4,5,6-hexasubstituted piperidine and tetrahydropyran from toluene. (c) 2015 Elsevier Ltd. All rights reserved.